2-amino-1 sulfonic acids



United States Patent 07 3,200,127 Z-AMINO-l SULFONIC ACIDS Donald L. Klass, Barrington, Ill., assignor to The Pure Oil Company, Chicago, 111., a corporation of Ohio No Drawing. Filed Oct. 24, 1960, Ser. No. 64,316 8 Claims. (Cl. 260-294.8)

' report the reaction of hexene-l with twice the molar quantity of dioxane-sulfur trioxide reagents to proceed as follows:

O\ SO:

Upon hydrolysis in cold water, this yields 2-hydrosulfatol-hexane sulfonic acid and this product yields, on further hydrolysis with hot water, 2-hydroxy-l-hexanesulfonic acid. To establish the mechanism of this hydrolysis reaction, these investigators investigated the reaction of hexane carbyl sulfate with aniline, followed by hydrolysis of the product, and found the following reactions to take place:

11-04Hn-CH-CH5 0 SO: CeH5NH] 2moles Furthermore, Bordwell and Peterson report that the reaction of hexene-l with 1 mole of SO -dioxane reagent forms:

and reaction of this product with 2 moles of aniline yields:

3,200,127 Patented Aug. 10, 1965 an illustration, the relationship of these reactions may be illustrated as follows:

1 mole dioxane-SOa e e ROH=CH RCHCHzSO3 NH;

2 moles NHz lbH 5 I 1 mole dioxaue-SO a NH NH III 11 Further reaction of the beta substituted sulfonic acid (I) with aqueous base yields the corresponding sodium salt (II). It is unexpected that the free acid (III), problNaOH ably in the form of Zwitterion internal salt, is obtained by treating an alpha-olefinic hydrocarbon with an equimolar amount of the sulfur trioxide complex, followed by treatment of the reaction solution with an equimolar amount of amine, instead of two moles of amine as reported by Bordwell and Peterson. Thus, it appears that a compound capable of donating a pair of electrons, in this case aniline, attacks the beta carbon atom first rather than the sulfonic acid oxygen atom. This means that compounds having the structural grouping:

where N is trivalent or tetravalent, can be prepared using the above scheme. Furthermore, I have also unexpectedly found that treatment of products of structures I and II with hydrochloric acid solution does not yield the hydrochloride of III as expected, but rather yields free compound III. Treatment of compound I and compound II with sulfuric acid also yields compound III. Thus, the beta anilinium sulfonic acid appears not to be basic enough to form salts with mineral acids. A similar phenomenon is encountered with sulfanilic acid. This compound gives only starting material from concentrated hydrochloric acid and. not the hydrochloride as one would expect. This behavior was observed when l-dodecene and l-hexene were used as starting materials. However, it should be pointed out that beta-amino groups derived from aliphatic and aralkyl amines would probably form acid salts.

During the course of the work with l-dodecene and l-hexene, I also discovered that the corresponding structures I, II and III'(with R as CH (CH are excellent surfactants, whereas the product I, where R was CH (CH had poor surface-activity properties. Likewise, products II and III prepared from I, with R as CH (CH exhibited poor surface-active properties.

It becomes therefore the primary object of this invention to provide a process for the preparation of betaaminated sulfonic acids and derivatives, a new class of surfactants having the formula:

Ra Ra R1-C- SO A it. Rr-IIT-(B);

Ru wherein R R R R R and R are the same or different substituents selected from the group consisting of hydrogen and alkyl, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic radicals containing up to 20 carbon atoms, A represents a cation such as hydrogen, a metal such as an alkali metal or alkaline earth metal, and tetravalent nitrogen, and B is an acid group, such as mineral acid (i.e., hydrohalic, sulfuric, nitro, phosphoric), with x being or 1, wherein when either R or R are aryl, x is 0; when R or R are alkyl, cycloalkyl or hydrogen, x is 0 or 1 by the foregoing reaction. In the case where x is 0, the nitrogen atom is not in the tetravalent state unless a tertiary amine is used or unless A is hydrogen, in which case the product exists as the electrically neutral form, or the Zwit-terion internal salt.

Regarding the novel surfactant products prepared from alpha olefins, the R group and products I, II and III must contain more than 4 carbon atoms if aniline is used as the amine or surface-active properties will be lacking. If R is equal to or is smaller than 4, the amine must be increased in molecular weight to give compounds exhibiting surface-active properties.

Another object of this invention is to provide novel surfactant compounds of the formula:

wherein R and A are previously defined.

These and other objects of the invention will be dea scribed or become apparent as the specification proceeds. In order to demonstrate the invention, a series of experiments Was conducted.

EXAMPLE 1 A l68-g. (1 mole) portion of l-dodecene was added to a complex prepared from 80 g. (1 mole) of sulfur trioxide and 88 g. (1 mole) of dioxane, in 200 ml. of ethylene dichloride. The addition was carried out at 0 C., with stirring, over a period of 1 hour. The resulting lightyellow solution was maintained at C. for two days, after which it was warmed to 0 C., and 186 g. (2 moles) of aniline in 200 ml. of ethylene dichloride were added. The resulting solution was maintained at 15 C. for two days, during which time Compound I (R was CH (CH precipitated. The precipitate was filtered from the liquid by the use of vacuum, and was dried with air to attain a yield of 181 g. A small sample of the product was recrystallized from water, resulting in the formation of small, White crystals having a melting-point range of 100-108 C.

EXAMPLE 2 A 3-g. portion of Compound I, in ml. of water containing 1.5 g. of sodium hydroxide, was warmed on a steam bath for 1 hour, after which the reaction mass was allowed to cool to room temperature, whereupon Compound II (R, was CH (CH precipitated as a fluffy, white crystalline product. The precipitate was recovered by filtration, and was air-dried, yielding 1.5 g. of a product having a melting-point range of 6770 C.

EXAMPLE 3 A 0.75-g. portion of product 11 was dissolved in 10 ml. of 10% hydrochloric acid, and the solution was heated on a steam bath for 1 hour. Then the solution was cooled 4 to room temperature, and Compound III (R, was CH (CI-I was recovered by filtration and dried, yielding 0.5 g. of a product having a melting-point range of 199-201 C.

EXAMPLE 4 The suds-forming and surface-tension-depressing abilities of the products of Examples 1, 2 and 3 were determined in soft and hard water. The results given in Tables I and II show all of these products to be substantially equal to or superior to a commercial detergent designated as Compound A.

Table I.--Suds-forming abilities of Compounds I, II, III in soft water 1 1 0.1% aqueous solutions of compounds I, II and III and a commercial detergent, Compound A, were prepared using distilled water.

2 Rating system. 1 to 10, 1=large volinne of suds, 10=no suds formed. Suds formed by hand-shaking a 4 oz. bottle 25 times with an equal amount of each 0.1% solution.

3 Compound A is not chemically similar to the surfactants of this invention, but was used as a commercially available example for purposes of comparison.

Table II.Suds-f0rming abilities of Compounds I, II, III in hard water 1 Suds formed at room temperature 2 Time to suds disappearance, hrs.

Appearance Compound 01 solution CompoundA P t 1 Compounds 1, II and III, and Compound A each at 0.05% concentrution in distilled water containing suflicient calcium chloride to make 360 parts/million as calcium carbonate.

2 Rating system. Same as in Table I.

EXAMPLE 5 A 168-g. (1 mole) portion of l-dodecene was added to a complex prepared from g. (1 mole) of sulfur trioxide and 88 g. (1 mole) of dioxane, in 200 ml. of ethylene dichloride. The addition was carried out at 0 C., with stirring, over a period of 1 hour. The resulting, lightyellow solution was kept at -15 C. for two days, after which it was warmed to 0 C. and treated with 93 g. (1 mole) of aniline in 200 ml. of ethylene dichloride. The resulting solution was kept at 15 C. for two days, during which time Compound III precipitated. It was identified by direct comparison with III above. The solid was recovered by vacuum filtration, and dried in air, resulting in a yield of 97 g. of crude III. The comparison sample after recrystallization had a melting point of 200-202 C.

EXAMPLE 6 The 97 g. of crude product III from Example 5 were dissolved in 500 ml. of water which contained in 30 g. of sodium hydroxide, and the resulting solution was successively warmed on a steam bath for 1.5 hours, cooled in an ice bath, and neutralized with 10% hydrochloric acid. During the neutralization step, an oil precipitated, and when the mixture was cooled still further, the oil phase solidified. This solid phase was recovered by filtration, washed with water, and recrystallized. The resulting product, designated as Compound IV, separated from the alcohol in relatively pure form as fluffy, white crystals which had a melting point range of 209230 C. (decom- 6 position). Six grams of the product IV were recovered ide. All experiments resulted in the formation of oily and identified as: products. For the purposes of measuring surface-active properties, the free acid was dissolved in distilled water (IV) 9 and treated with an equimolar amount of aqueous sodi- CH (OH2)aCHCHzSOaNa 5 um hydroxide solution to give 0.1% aqueous solutions 9 of sodium salt. Each of these compounds from Ex- OSOaNa amples 8, 9 and were examined for surface-active properties as 0.1% aqueous solutions. Unlike the comby analyses and i f d Spactra pounds prepared from dodecene-l, these products ex- 10 hibited little or no surface-active properties. All of the EXAMPLE 7 surface tensions were greater than 50 dynes/cm. and

suds ratings were 8- to 10. A 0.75-g. portion of product I above was dissolved in In order to identify and establish the formulas of the 10 ml. of 10% hydrochloric acid solution, and the solllvarious compounds that were prepared, selected ones tion was warmed on a steam bath for 1 hour. The resultwere analyzed, tested for unsaturation, and their melting product, designated as product III, was recovered by ing points were determined after purification. The refiltration, and had a weight of 0.55 g. and a melting point sults are shown in the following table:

of 1'98200 C. It was identical to the product obtained Table In from l-dodecene by treatment with an equimolar amount of sulfur trioxide-dioxane complex and subsequent treatment with twice the equimolar amount of aniline, followed Compmmd I H m N by treatment with sodium hydroxide and treatment of the 0 resulting product with hydrochloric acid. g gg fig iaf; 103-106 a; at EXAMPLE 8.--(ANILINE SALT OF Z-ANILINO- 7.38 HEXANE-l-SULFONIC ACID) N 2 66.8 54.5 The known prior art procedure of Bordwell and Peter- 3-? 3-3 son was used. l-hexene (21.5 g.) was added to the complex prepared from 20.5 g. sulfur trioxide and 22.6 g. of E--- di-oxane at C- in 75 of ethylene dichloride The i ih e ie Sfi EiIIIII po ive poiiive poggive po itive mixture Was stirred for minutes and then 50.0 g. of aniline was added dropwise. A white precipitate formed 1 CHHNOaNZg at the end of the addition. The mixture was kept at room CWHWOJNSNa-ZHZO- Since the mere fact that a compound forms a foam with water and/or lowers the surface tension of water does not always indicate that the compound will funcanlhne salt of 2-an1l1no-hexane-l-sulfomc acid, as white tion as a detergent, a Series of experiments were com needles, Bofdwell a ducted with carbon black suspensions in dilute aqueous Peterson r p rted MP. 10 11 C- ThlS p t 18 solutions with some of the foregoing products. The with CH (CH as R results are summarized in the following table.

temperature for 3 days, filtered, and the precipitate was washed with ethylene dichloride and air-dried, wt. 40.1 g., M.P. 80-92 C. Ten g. recrystallized from about 200 ml. of water and 10 ml. of alcohol gave 8.0 g. of the pure Table I V.-Rate of Carbon Black Settling I. IV.

Time Water Control CH; (OHg)nC|lHCHzSO NH; olrnorrpu zHornsofirm sofl Na 0 15 min Afi i r s t? clear 0mg}: 30 min Clear Do. 1 hour -do do Do. 2 hrs .do .Slight clearing Do. 3 hrs do do Do.

EXAMPLE 9.(2-ANILINO-HEXANE-1- In conducting these experiments, 100 ml. of 0.1% SULFONIC ACID) aqueous solutions of the compounds and 100 ml. of

- 'th 1.0 of Norit A carbon black Crude aniline salt from Example 8, 2.5 g. (0.00715 Water were treatgd mole), was treated with 69.2 ml. of 0.1033 N hydrochloric and handshake? 25 a smPPered; f grad acid (0.00715 mole). Evaporation on the water bath Hate observat'lops were made Penodlcany of the under nitrogen to about 15 ml. gave the free sulfonic acid. Supernatant solution and partlples suspended above the The product was filtered, washed with a small amount of h of carbon black if fi F to the bottom ether, and dried, MR This product is In with-1n 15 minutes. The term clear 1n the table means with CH3(CHZ)3 as RP that about 99% of the carbon black has settled to the bottom of the graduate and the term opaque means EXAMPLE 10' (SODIUM ZANILINO'HEXANE that a stable suspension of cleansing action was obtained. SULFONATE Table V sets forth a number of species of compounds Attempts were made to prepare a crystalline sodium by formula and name coming within the definition of the salt by treatment of the aniline salt with sodium hydroxprocess invention.

The olefinic starting materials for the reaction have been in part defined by the examples of the beta-aminated sulfonic acids that can be prepared in accordance with this invention. Any compound containing an olefinic double bond may be used to prepare the sulfonic acids of this invention. The only limitation attaching to the substituent groups R to R4' inclusive, is that these substituent groups are not reactable with the sulfur trioxide complex used under the conditions of the reaction necessary to cause reaction with the olefinic double bond. The various sulfur trioxide complexes that may be used in this reaction have difiering reactivities and some require elevated temperatures. Under some conditions, the intermediates may decompose faster than the beta-amination reaction can proceed, in which event the yields of beta-aminated sulfonic acids may be lowered. Where the R to R groups are saturated alkyl radicals or cycloaliphatic radicals, no difficulty is experienced due to sulfonation occurring in the substituent group. Where the R to R groups are aryl, heterocyclic, or other slightly reactive groups that may sulfonate across a double bond within its structure, the reaction of this invention will still take place but certain precautions are necessary to prevent sulfonation of the substituent group. This is easily overcome by the choice of sulfur trioxide complex and the reaction temperature. The only disadvantage attaching to the use of the more complex aromatic, heterocyclic, or other somewhat reactable substituents, is that lower temperatures may be necessary and the reaction time is extended.

Accordingly, the following additional olefinic starting materials may be used in the reaction of this invention:

4-methyl pentene-l, 3-methyl pentene-l, 3,3-din1ethyl butene-l, isopropylethylene,

l, l-diphenylethylene, Z-methylbutene-l, heptene-l,

heptene-2,

heptene-3,

octene-l,

tetraphenyl ethylene, triphenylethylene,

sym. diphenylethylene, 3,3,5,5-tetramethylheptene-1, isooctene, -methyl-6-ethyl-4-N-propyloctene-3, tetramethylethylene, 3,3-dirnethylbutene-l, 3,3-dimethylhexene-4, 3,3,dibutylhexene-4, 3,3,dipropylhexene-4, 2,2-dimethylhexene-3, unsym.-diisopropylethylene, 2,3,4-triethylpentene-2, 2,3,4-trimethylpentene-2, 2,2,3-trimethylpentene-3, 2,3,3-tripropylpentene-l, 4-methylhexy1ene- 1, l-decene,

l-dodecene,

2-hexene, Z-methyl-Z-hexene, S-methyl-Z-hexene, 4-ethyl-2-hexene, 5-methyl-2hexene, 3-hexene, 2,5-dibutyl-3-hexene and 2-methyl-3-hexene as known olefinic hydrocarbons.

Other starting materials include phenyltrimethylethylene, phenyltriethylethylene, phenyltributylethylene, phenyltripropylethylene, phenyltriisopropylethylene, phenyltriamylethylene, phenyltrihexylethylene, phenyltricyclopentylethylene, diphenyldimethylethylene, cliphenyldibutylethylene, diphenyldiisopropylethylene, diphenyldicyclohexylethylene, methyltriphenylethylene, butyltriphenylethylene, propyltriphenylethylene, 3-rnethylphenyltrimethylethylene, naphthyltrimethylethylene, dinaphthyldimethylethylene, 2-butyl-3-phenylpentene-2, 2,3-diphenylpentene-Z, triphenylbutene-l, Z-i-sopropyl-3-naphthylpentene2, 2,3-dinaphthylpentene-2, trinaphthylbutene-l, benzyltrimethylethylene, dibenzyldimethylethylene, naphthyldimethylethylene, 2-methy1-3-furylpentene-2, 2-methyl-3- thienylpentene-Z, 2-propylthienylpentene-2, 2-butyl-3- furylpentene-Z, trianthrylbutene-l, dianthryldimethylethylene, dianthryldiisopropylethylene, 2-hexyl-3-thienylpentene-Z, 2-cyclohexy1-3-thienylpentene-2, and 2-cyclohexyl-3-furylpentene-2.

The nitrogen compound used in the second step of the reaction may be any nitrogen compound capable of donating a pair of electrons to the beta carbon atom of the olefinic starting material. The preferred groups of nitrogen compounds have the formula:

s wherein R R and R are the same or different saturated, unsaturated, straight-chain or branched-chain alkyl radicals, hydroxy-alkyl radicals, hydrogen, cycloalkyl radicals, hydroxycycloalkyl radicals, phenolic radicals, or aryl, aralkyl and heterocyclic radicals containing up to 20 carbon atoms. Where R R and R are hydrogen, am-

monia is the reactant nitrogen compound. Where one R group is a hydrocarbyl radical, the class of primary amines is defined by the formula. Where two of the R groups are hydrocarbyl radicals the class of secondary amines is so defined, and where all three R groups are the selected hydrocarbyl groups the general class of tertiary amines is included.

Species of nitrogen compounds include:

Methylamine Isohexylamine Dimethylamine Hepthylamine Trimethylamine Triheptylamine Pentylamine Octylamine Dipentylamine Dioctylamine Tripentylamine Nonylamine Ethylamine Decylamine Diethylamine Dodecylarnine Triethylamine Trihexylamine Propylamine Cyclohexylamine Dipropylamine Dicyclohexylamine Triproylamine Tricyclohexylamine Butylamine Cyclopentylamine Dibutylamine Dicyclopentylarnine Tributylamine Tricyclopentylamine Isopropylamine Methylethylamine Diisopropylamine Dimethylethylamine Triisopropylamine Diethylmethylamine Isobutylamine Ethylpropylamine Diisobutylamine Methylpropylamine Triisobutylamine Propylbutylamine Amylamine Isopropylisobutylamine Isoamylamine Benzylamine D-iisoamylamine Ethyldecahydronaphthyl- Triisoamylamine amine Tertiarybutylamine Propyldecahydronaphthyl Ditertiarybutylamine amine Tritertiarybutylamine Diethylcyclohexylamine Undecylamine Dimethylaminoethylamine Decylamine Dioctylibutylamine Diamylisopropylamine Dinonyloctylamine Diamylhexylamine Didecylpropylamine Dihexylamylamine Didodecylbutylamine Diheptylmethylamine Dioctadecylamylamine Hexylamine Aniline N-oleyl ethylamine Diphenylamine Phenyl-a-naphthylamine Di-ot-naphthy1amine N,N-diphenylbenzidine Phenyl-tolylamines N,N-ditolylbenzidenes 2-aminol-ethanol 2-amino-3 -butanol 3-amino-4-pentanol Triphenylamine Phenyl-fl-naphthylamine Di-B-naphthylamine N,N-di-,8-naphthyl-pphenylenediamine N,N'-diphenyl-pphenylenediamine Ditolylamines Tolyl-naphthylamines N,N-ditolyl-p-phenylene- Z-amino-I-butanol p-propylthiocyclohexyl- Z-aminol-pentanol amine Laurylamine Cyclohexanolamine Guanidine 0,0'-dihydroxydicyclohexyl- Oleylamine amine Eicosenylamine The cation represented by A in the formulas may be any cation which will associated with the sulfonic acid group and may be hydrogen, sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, or tetravalent nitrogen as the preferred class where compounds having utility as surfactants are desired. Other examples of the A group include arsenic, antimony, bismuth, chromium, molybdenum, tungsten, manganese, iron, cobalt, and nickel. It is to be observed that A may also be any of nitrogen compounds aforementioned as reactants with the nitrogen in a tetravalent state. Ammonium hydroxide may be used as the reactant cationic material. The reaction forming the compounds of type I, wherein 2 moles of the nitrogen compound reactant are used attaches same to the sulfonic acid group and to the beta carbon atom of the olefin starting material.

The various basic salts or hydroxides that may be used to transform compounds I into compounds II are the oxides and hydroxides of the foregoing metals, i.e., sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, barium oxide, barium hydroxide octahydrate, and ferric hydroxide.

Any inorganic or organic acid may be used to transform the initial reaction products I or II to compounds of type III. The inorganic acids to be used are hydrochloric, hydrobromic, hydroiodic, hydrofluoric, sulfuric, nitric, carbonic, and sulfurous acid, and the like. The organic acids include acetic, propionic, benzoic, lactic, citric, oxalic, butyric, hydrocyanic, malonic, oleic, succinic, laur-ic and valeric acid, and the like. Any acid capable of producing hydrogen ions may be used for these steps of the reaction.

The reaction is carried out by merely bringing together the olefinic reactant with the sulfur trioxide complex at temperatures best suited for the particular complex employed. In general, sulfur trioxide complexes react at temperatures between to 120 C. A number of Cit sulfur trioxide complexes are available for the reaction. Dioxane-sulfur trioxide, trimethylamine-sulfur trioxide, pyridine-sulfur trioxide, triethylamine-sulfur trioxide, di- Inethylformamide-sulfur trioxide, dioxane bis-sulfur trioxide, thioxane-sulfur trioxide, thioxane bis-sulfur trioxide and dimethylaniline-sulfur trioxide complexes may be used. There is a threshold temperature at which each complex becomes reactive. Consequently, the most suit able temperature range for the reaction will depend somewhat on the complexing agent used. The most suitable temperature range between 10 to 120 C. may be found by trial experiments. In general, the reactivities of the complexes is known in the art, and as in the case of pyridine-sulfur trioxide, a temperature between about to C. is suitable. It may be found that the intermediates decompose faster than they are formed, in which event lower temperatures and longer contact times will be necessary.

The reaction time may be from five minutes to one day and no pressure is required. Since the complexes are solids, they are used in solution or slurry form with an inert solvent. Suitable solvents include ethylene dichloride, ethylene trichloride, various organic esters such as ethyl acetate, butyl acetate, propyl acetate, unreactive naphthas or mineral oils, mineral spirits, VM & P naphtha, Stoddard solvent, and cyclohexane. With dioxane-sulfur trioxide as the reactant complexing agent, one expedient is to use an excess over the stipulated 1 molar quantity whereby the excess acts as a solvent for the reaction. Other of the complexing agents may be used in this manner.

Agitation is applied to the reaction in a known manner or may be omitted, although its use shortens the reaction time.

A color change will be observed generally as an indication of the completion of the first stage of the reaction. Various other expedients, such as detection of unreacted olefin or complex, may be used to follow the reaction and determine when equilibrium has been reached.

The addition of the reactant nitrogen compound in the second step of the reaction is conducted gradually with continued agitation. This stage of the reaction is easily followed since the beta-aminated products are solids and precipitate from the reaction mixture. Various known methods of separating the solid product may be used. Filtration under vacuum is one expedient, and centrifuging or setting may also be used. The product may be used per se without separation and recrystallization although for most uses it is the better practice to separate and purify the end products. The products may be recrystallized from any of the solvents mentioned herein or water may be used for this purpose. Identification is made through melting points, mixed melting points, refractive index, infrared analyses or analyses for the elements. The reaction may be conducted batchwise or on a continuous basis.

The step of acidiying the reaction product, where the alternative procedure of using 1 mole of sulfur trioxide complex with 2 moles of nitrogen compound is used, is readily carried out by adding a stoichiometric or excessive amount of any material capable of producing hydrogen ions in aqueous solution. The organic or inorganic acids disclosed herein are added in concentrated or diluted solutions to the reaction mixture and the pH is adjusted on the acid side. The reaction products from this alternative procedure are separated as before described in connection with the direct method using 1 mol of complex with 1 mole of nitrogen compound.

As many apparently widely different embodiments of this invention may be made without departing materially from the spirit and scope thereof, it is to be understood that the invention is not limited to the specific embodiments thereof except as defined in the appended claims.

The embodiments of the invention in which an exclu- 13 sive property or privilege is claimed are defined as follows:

i1. Surfactants of the formula Rn-(fH-CHr-S 0311 wherein R is alkyl of 6 to 20 carbon atoms.

14 -7. A compound of the formula wherein R is .a-l'kyl of 6 to 20 carbon atoms and A is an alkali metal.

8. A compound of the formula R1-CHCHZSO3NH3 wherein R is alkyl of 6 -to.20 carbon atoms.

References Cited by the Examiner UNITED STATES PATENTS 12/41 Hentrich et a1. 260-503 1 2/ 54 Stayner 260-508 2,917,512 1'2/59 Hel ferich et .al, 260-508 FOREIGN PATENTS 5/ Canada. 1,161,528 9/58 France.

815,167 6/59 Great Britain. 856,404 12/60 Great Britain.

OTHER REFERENCES Mustafia: Chemical Reviews, vol. 54, No. 2, pp. 223 (1954).

Bord-well et al.: JACS, vol. 76, pp. 3945-3961.

IRVING MA'RCUS, Primary Examiner.

WALTER A. MODANCE, Examiner.

12/58 Davies et a1. 260-503 

1. SURFACTANTS OF THE FORMULA 